Wetting agent



Patented Dec. 3, 1935 UNITED. STATE W rma AGENT;

Benjamin E. Harris, Chicago, Ill;

No Dating. Application ember- 31,1932, Q 7

Serial No. 640,501; 23 Claims. (cizszyj My invention relates to a new class of chemical substances, and more in particular to a new'class of chemical substances particularly adapted for use for detergent, penetrating, emulsifying, lathering flotation, anti-spattering or ,frothing purposes or reducing the surface tension of water. In certain classes of industries, there is a need for a certain class of chemical substancesusually used in relatively small quantities .but capable of use in larger quantities to secure an effect principally the result of-a wetting action such as at a water-oilinterface. In the textileand leather treating industries, for example, there are many situations where'a wetting Qr detergentaction is imperative and many different chemical substances have beenproduced calculated to reduce surface tension and promote wetting in these industries. The use of prior art substances has not been attended with unqualified success in all instances. In certain other types ofindustries, such as the margarine industries, for example, problems in preventing the spattering of margarine in frying have arisen.

In one of my copending applications, I have described a new class of substances possessing certain properties which lend themselves to be used in connection with oleomargarine to prevent the spattering of the oleomargarine during frying.

portions of the emulsion at the interface thereof.

Although the problem is probably not one of wetting action entirely, it appears that certain compounds, which I described iii-my copending application, having the properties of concentrating at the water oil interface, willhavean effect upon the spattering behavoir of, magarine. In view ofthe fact that many of the substances, which I have-discovered and. described inn my copending application, have a certaineifct upon surface phenomena and are ofa colloidal *or'se'micolloidal nature, I have also found them useful in many other industries functioning as "softening, wetting, emulsifyin detergent, lubricating, frothmg; and penetrating agents in the arts where such agents are employed.

The principal object of my present invention stances capable of satisfactory use in connection withthe-problems;hereinabove'discussed."

Another object is the provision of a new class group may stand in relatively closer proximity'jto groups." 'I' have pointed out that "if the hydromilk andoleaginous material.

of relatively simple structureand can cheaply made in commercial quantities. I

Another object is the provisionof a class of chemibal substances ofthe character set forth which in many instances will be innocuous and Hnonetoxic, eventhough employedinfsuch foods as margarine.

' Anotherobject is of a new' cl'ass of chemical substances having improved wetting 10 characteristics.

YAnothe'r objectfis. the smart; new cast,

- -i ub n es ,iwim r til t n he t a n of'textileimaterials. J k

theriobjects and features ofthe invention willlbef app ren from a consideration. of the following detailed description.

s saaah which 1am concerned are designatedas hydrophillic lipi'ns. "one of theoutstanding characteristics of the substances is the presence of lipophile and hydrophilejgroupsin the molecule. ,Apo rtion, of the moleculehas groups which are easily wettedbyjoils. This lipophile group in the sub-- stances which I have investigated is aradi'cal of predominately hydrocarbon I characteristics,

though itjmay'al'sobe an'alcohol, ether or ester "group, or some other. groupasjwill appear from the illustrationsfgiven below; The lipophile group has' jn'iarked aflinity for oils' and I fats, is readily capable of being 'wet by oleaginous media, and, in general, v at v the water-oil interface, tends to caus'ethe" molecule,"of which it is a part, soto orientate itself; apparently, that the lipophile the oil medium or phase, as'contrasted" With-131 36 aqueous medium. The hydrophillicf portionf'bf the molecule is a group whichjis easily wetted by waterrand among these groups'are such groups as OH groups or OH groupsv sulphate 40 phillic lipin' contains a 'hydrophile' group which will sufficiently balance the lipophile g'roug then' such substance when use'dfin small proportions will act as v an antispatterei' 'preventing thespattering during frying fof'margarine ade"from 'p erly: offs teandzbalance theichydrophfllii' c 1s the provision of a new class of chemical subof chemical substances which greigggneral margarine emulsion and hence (assuming the employment of the substance in a margarine emulsion), largely loses its anti-spattering power. The above is merely a hypothesis which appears to fit the discovered facts and helps to explain them.

Chemically, the substances of my present invention are in general ester derivatives of moderately high or high molecular weight fatty acids or ether derivatives of moderately high or high molecular weight alcohols, with at least onesemi-esterified sulphuric acid group. In certain circumstances, there may be more than one semiesterified sulphuric acid group or there may be sulphuric acid groups that are totally esterifled and other sulphuric acid groups that are semiesterified, but in all cases there must be at least one semi-esterified sulphuric acid group.

Considering the compounds from another aspect, the molecule in each instance contains a relatively high molecular weight lipophile group or groups and a hydrophile group or groups which, in the class of compounds to which my present invention relates, are principally sulphuric acid radicals. From still another angle, the compounds may be considered as combinations of a higher molecular weight lipophile group and the sulphate group linked together by means of a third group which is generally a poly-hydroxy organic compound with at least two esteriflable hydroxy groups. A more complete understanding of what may comprise the lipophile groups and the intermediate radical which links the hydrophile group to the lipophile group will be had as the detailed description progresses.

I, therefore, have a substance containing a sulphate group and a lipophillic group of a sufficient molecular weight to balance the sulphate group. This substance may be a good anti-spattering substance when used in connection with margarine if the balance" is sufiicient; or it may function well in other industries as a wetting, penetrating, emulsifying, frothing, or detergent agent.

The function of the sulphuric acid groups is to impart hydrophillic properties, that is, water wetting or water attracting properties, to the molecule as a whole. The groups with which the sulphuric acid group is linked are in general of a lipophile character. At times they may be strongly lipophillic and at other times moderately lipophillic. They may be of comparatively low molecular weight or of moderately high molecular weight or of distinctly high molecular weight, dependingupon the purpose for which the substance may be used. Furthermore, the group or groups with whichthe. sulphuric acid is esterified may have hydrophillic radicals of their own. An example of this type of substance is lauryl glyceryl sulphate (sodium salt) It is evident that in the above substance the molecule which is esterified with sulphuric acid is monolaurin, which happens to have a hydrophillic radical of its own, namely, the unesterified hydroxy group in the glycerol residue;

It should also be observed that the lipophile function in the above molecule is dependent principally upon the lauryl group. The hydrophile function is dependent principally upon the sulphate gro'up. Furthermore, these two groups are linked together by means of a poly-hydroxy substance, namely, glycerol.

Some additional examples of members of the group of substances which I have discovered are as follows:

0 HzC-O-( L-CnHu 0 Mono-oleyl dlethylene glycol lgilphate (potas- I IIz-C-O-l-CnHa Palmityl glycerol phate (sodium salt) sul- Mono-oleyl trlatliylene o I mo-o-e-cum,

H H: -CHrO- 3 =0 Lauryl mmemynne glycol sulphate (sodium salt) Sulphonated monostearyl glucose.

lycol sulphate (sodium salt) Palmityl glycerol sulphate H |-CH:-OS=O 0 Mono-oleyl triethylene gly- Jjj col sulphate 60 HaC-O- CnHu 0 Lauryl trimethylene glycol sulphate I ll H:C-COC.CNH21 Myristyl propylene glycol sulphate While the above list of the illustrative embodl- Octoyl diglyoerol sulphate Csproyl ethylene glycol sulphate mht. la

0 H:C0 -'-CiHn Caproyl ethylene glycol gialilshate the material which is to be esterified with the ments of my invention indicates single, pure sub stances only, it must be understood that mixtures may very well be used, either mixtures of single substances prepared independently or mix- 5 tures produced as such, that is to say, instead of esterifying diethylene glycol with lauric acid and then esterifying the resultant ester with sulphuric acid, I can employ a mixture of coconut fatty acids, such as is obtained from coconut oil, and 10 esterify this mixture of fatty acids with diethylene glycol to form a mixture of the mono fatty acid esters of diethylene glycol. This mixture I then esterify with sulphuric acid to give me the finished product. 15

As sources of the lipophile group I can cmploy, for example, such materials as melissic acid, stearic acid, oleic acid, ricinolelc acid, lauric acid, palmitic acid, I cetyl alcohol, lauryl alcohol, cholesterol, mixed coconut fatty acids, mixed tal- 20 low fatty acids and other materials withmarked aflinity for oils and fats.

For the purpose of linking the lipophile groups with the sulphate groups I can employ such' molecules as glycerol, diglycerol, polyglycerols, glycols, 25 polyglycols, hydroxycarboxylic acids, sugars, alcohol derivatives of sugars, acid derivatives of sugars, and other diand poly-hydroxy organic substances.

For the purpose of introducing the sulphate groups I may employ sulphuric acid, concentrated or fuming, chlorsulphonic acid, sulphuryl chloride, sulphur tri-oxide, solutions of sulphur trioxide and other so-called sulphonating agents. The treatment with these agents may take place 35 in the presence or absence of solvents and condensing agents such as pyridine and the like.

The method for introducing the sulphate group difiers in different cases and is dependent upon 40 sulphuric acid and the purpose for which the resultant product is to be employed.

An example of one of my methods is as foltion inasmuch as under these conditions the fat 5 material separates in a distinct supernatant lay- I er and facilitates the separation of the wash water in each successive washing. The product thus obtained contains a considerable proportion of water and in addition to the principal product, namely, monostearine sulphate (sodium salt), contains besides, some unreacted monostearine and free stearic acid. If desired the substance may be purified. I

Monolaurin and other mono fatty acid esters of glycerol and other hydroxy organic substances may likewise be, treatedv by the procedure just described.

Still another satisfactorymethod is the one I followed in preparing lauryl 'diethylene glycol '7 sulphate (ammonium salt) which is as follows:

10 parts by .volume of monolauryl diethylene glycol dissolved in 20 parts by volume of chloroform are cooled in ice water. 1 /2 parts by volume of chlorsulphonic acid dissolved in 10 parts 75 ture of the reaction mixture appreciably.

by volume of chloroform are now slowly added with vigorous stirring to the first chloroform solution, at such a rate as not to raise the tempera-er AI all the chlorsulphonic acid solution has been introduced, the reaction mixture is aspirated with adryinertgas,tocarryoutmostofthehydrochlorlc acid formed during the reaction. Finally, ammoniagasispassedintothemlxturetoneutrality. The chloroform may then be distilled oil or evaporated. The product thus obtained has a remarkable power for lowering the surface tension of water, even at very low concentrations, and has many other useful properties of the character described in the early part of the specification.

Those of my substances which are freely soluble in "water may be recovered from their solutions in the customary manner by concentrating and crystallizing. As the mass of the lipophile radical increases, solubility in water tends to decrease and aflinity for water is manifested by dispersibility in water. From these aqueous dispersions my substances may be readily recovered by salting out" with suitable soluble electrolytes- Common salt is very satisfactory for this purpose in most cases. when salted out of an aqueous dispersion at temperatures ranging from 60 to 95 0., the substances are obtained in the form of a paste with a water content ranging from approximately 25 to '75 percent. The more bydrophyllic the substance, the greater the water content and, of course, the salt is present in the water of the paste in approximately the mine concentration in which it existed in the dispersion from which the product was salted out. The product maybe treated to remove the salt.

Although, in many respects, the compounds of my invention differ from each other in accordance with the numerous examples given and description of the variations in their properties, nevertheless many of them may be represented by the structural formula wherein R is an alkyl, acyl, or some other lipophile group, O is oxygen, X represents the residue of a polyhydroxy substance which links together the lipophile group with the hydrophyllic sulphate group, 8 stands for sulphur, Y is a cation, and w and v are small whole numbers, at least one.

I have also found that the addition of certain materials to the substances with which my invention is concerned, as hereinabove described,

markedly enhances their capacity to lower the surface tension of water, their serviceability as wetting-out agents'. in the textile heating industry, and markedly improves many of their other valuable colloidal properties. These ad dition agents are principally the more or less lipophile ethers and esters of the hydroxy organic substances which I employ for with sulphuric acid or its equivalent in order to I Y- havingatleastonefreeOHgroup. Whilethesehydrophylliclipinshrmaymthemf. fidmtlybalamedtohaveamarkedeifecteitherto preventspatteringofordecrease 5' interfacialtenfioninwater-oilemulsionsasmthe caseofthehydrophylliclipinscontainingasemieffectofso thesnrfacephenomenaof thelatterincmtactwithanaqmousmedimnsolo astoaifecttheinterfadalslnfmsurfacetensionand the penetratingand wetting properties.

I have made extensive experiments to determinetheelfectoftheadditionagentsinincreasingthewetting ofrnynevvsulphatelfi compounds. It will be t for an understandingofthis'phaseoftheinventiontogive afewillmtrative Inthecaseofmonoolemdi-sulphatewhichinitselfisagoodwetfingagmLIfoundthatforsomeof-zo themono-olein di sulphate inthetreating bath tely 40% of mono-oleyl die y glycolgreatlyimproved wetting acfion. Forexampleinthecaseofthemono-oleindisulphate, one-tenth of a gram dissolved in25 100 cc. of watershoweda surface tension offll dynes per centimeter. with six one-hundredths of a gram of mono-olein di-sulphate and four one-hundredths of a gram of monn-olein diethyleneglycolalsodimolvedhilflfl cc.ofwater, 30 Ifoundthatthesurfaeetensionwas to iidynespercmtimeter. Inthesameway,I foundthatwhilesulphatesofmixedcoconutfatty acid esters of diethylene glycolwere good wettingagentathewetfingactionwasgreatlyin-ES creasedbytheadditionofaprcportionofmonm oleyldiethyleneglyeol. Inthecaseofmonolaminsulphateusedasawetlingagent,1fo1md that I also obtained improved results by the usetherewithofaproportionofmono-caprym lo Thesurfaeeofwaterunder theconditionsinwhichtheabovedatawasistablishedwas 'l ldynespercentimeter. Byoneofthe sulphate compoundsof mypresentinvention and asuitableagmtoftheclasshereimbovefi I have found flnit very much. better wetting of anyotharknownwettingagentwithwhichl amfamiliar.

Itwillhemtedthat whilemysulphuricestersfll inproduceaeloweringof. surfacetenn'omthiseifectis enhancedbythe addition of the fatty acid steranctwithstanding the fact that the concentration of the sulphuricesterproperis Itistohenotedthatwhilelhavechosenthe lowering of the surface tension of water as a convenient means of illustrating the effect of these addition agents, this surface tension loweringis bynomeans theirsole eifect asthey' radically other valuable colloidal characteristics of the medium into which they are introducedaswefl asgthesurfacetension.

ThewhichI addtomysulphuric estersfor thepurpose ofenhancing their useful colloidal properties, may be represented by the structuralformula:

group,Oisoxygen,Hishydrcgen,wisasmall whole number, at least one, and X represents 7 which it is used, and the relationship of the improved compounds of my invention thereto, I wish to point out again from the standpoint of its terminology the manner in which the compounds of my present invention are produced.

I select preferably in the first instance a compound (or in some cases a mixture of compounds) which has both a lipophillic group and a hydrophillic group. Thecompounds which I employ initially, however, are dominantly lipophillic, the hydrophile group, in most cases for example a single OH group, being of insuflicient strength or character to affect the more dominant lipophile group to any great extent. I then attach to the lipophile group, preferably at a hydroxy or carboxyl group, a hydroxy or poly-hydroxy sub stance which in itself has some hydrophillic characteristics. A suitable example as previouslyset out are glycerols and glycols and poly,- compounds thereof. I then attach a sulphate group to the hydroxy radical by sulphonation, as previously described.

Substantially any process employed in producing the improved compounds of my invention yields a material having a proportion of water mixed therewith. In most cases the material is suitable for use in this condition without being dehydrated. It can be dispersed readily in additional amounts of water down to concentrations of, for example, one-tenth per cent. as in the illustration given above. In certain cases, however, the materialmay require dehydration either partially'or entirely. Due to theirlpronounced hydrophillic properties, these'materials, however, tend to retain some moisture in'them even under very rigorousdehydration treatment so that except in extreme cases it may be said that the materials always have a proportion of moisture present.

It will be noted that while the strictly rigorous sense of the term sulphonation denotes the introduction of a sulphonic acid group, I have used this term throughout in the sense that it is employed technically in the industries. In every instance, sulphonation as employed in this specification denotes the formation of an ester of sulphuric acid.

I have described my invention in detail in order that those skilled in the art may practice the same, but it is obvious that I do not restrict myself to the specific details described, the invention being limited only by the scope of the stance, is reacted with a fatty acid, such as lauric acid, to produce a mono-ester and is then treated with sulphuric acid or the like to produce mono laurin mono sulphate, the "residue of the polyhydroxy substance is 'cnon Throughout the specification and claims. the term residue"i s to be regarded as r the above connotation. I v What I claim as new and desire to protect ,by Letters Patent of the United States is:

1. A stable chemical substance represented by the general formula wherein R is an acyl radical with at least four carbon atoms, X represents the residue of an aliphatic polyhydroxy substance of a class consisting of glycerol, polyglycerols, glycols, polyglycols, hydrcxycarboxylic acids, sugars, sugar alcohols, and acid derivatives of sugars which links together the acyl radical with the sulphate group, Y is a cation, and w and v are small whole numbers, at least one. 1

2. A stable chemical substance represented by the general formula wherein R is an acyl radical with at least four 40 carbon atoms, X represents a residue of a glycol which links, together the sulphate group with the acyl radical, Y is a cation, and 'w and v are small whole numbers, at least one.

4. A chemical substance represented by the general formula v o R-OX --os:-o Y,

50 wherein R is an acyl radical of a fatty acid with at least four carbon atoms, X represents a residue of diethylene glycol which links together the sulphate group with the acyl radical, Y is a cation and w and v are small whole numbers, at least 55 I one.

5. A chemical substance represented by the general formula wherein X represents a residue of an aliphatic polyhydroxy substance of a class consisting of 5 glycerol, polyglycerols, glycols, polyglycols, hydroxycarboxylic acids, sugars, sugar'alcohols and acid derivatives of sugars which links together the oleic acid group with the sulphate group, Y is a cation, and w and v are small whole numbers, at 70 least one.

6. As a new chemical compound, mono-olein disulphate.

'7. As a new chemical compound, mono-oleyldiethylene glycol sulphate. I

8. Ah'eaflngbathcomprisinganaqueous liquid havirg flpersed therein a stable ester of sulmm'leaeldoftheseneral formula" 4 Rankin}.

wherein B an. acyl radical with at least romcarbon atoms, x represents the residue of an alifliatic polyhydroxy substance of a class conwherein R is an acyl radical with at least four carbon atoms, X represents a residue of glycerol which links together the sulphate group with the acyl radical, Y is a cation, and w and v are small whole numbers, at least one.

10. A treating bath comprising an aqueous solution having dispersed therein a relatively small amount of esters of sulphuric acid of the general whereinRis an acyl radical with at least four carbon atoms, X represents the residue of an aliphatic polyhydroxy substance of a class consistf y r p lyslycerols, s y p ve yw hydmxycarbomlic sugars, sugar alcohols and acid derivatives of sugars which links together the acyl radical with the sulphate group, Y is a cation and w and n are small whole numbers, at least one, and including as an addition agent a relatively sinah amount of a hydrophillic lipin of the general formula n-ox -011)- whereinltis an alkyl or any! radical, w is asmall whole number, at least one, and X represents a residue of an aliphatic polyhydroxysubstance with at least one free hydroxy group.

11. Ahydrated mixture of an ester of sulphuric acid of the general formula wherein R is an acyl radical with at least four carbon atoms, X represents a residue of an aliphatic polyhydroxy substance of a class consistene glycol and salts thereof.

ing of glycerol, polyglycerois, glycols, polyglycols, hydroxycarboxylic acids, sugars, sugar alcohols and acid derivatives of sugars which linkstogether the acyl radical with the sulphate group, Y is a cation and w and v are small whole numbers, at 5 least one, andincluding a hydrophillic lipin of the general formula I j a wherein R is an alkyl or acyl radical, in is a small 10 whole number, atleast one, and X represents a residue of an aliphatic polyhydroxy substance with at least one free hydroxy group. 12. A hydrated mixture of mono-olein di-sulphate and mono-oleyl diethylene-glycol. 15

13. A mixture containing, sulphates of mixed mono-coconut fatty acid' esters of diethylene glycol and mono-oleyl diethylene glycol.

14. A mixture containing mono-laurinsulphate and mono-caprylin.

,15. An ester of sulphuric acid and an aliphatic 'polyhydroxy substance with at least two esteriflable hydroxy groups, wherein the hydrogen of at least one hydroxy group is replaced by a sulphate radical, and wherein the hydrogen of at least one 2 other hydroxy group is replaced by an acyl radical with at least four carbon atoms, said ester having hydrophillic properties, and wherein the other hydrogen of the sulphate radical is replaced by a cation. l 16. An ester of sulphuric acid and an aliphatic dihydroxy substance wherein the hydrogen of one hydroxy group is replaced by a sulphate radical, and wherein the hydrogen of the other hydroxy group is replaced by an acyl radical with at least four carbon atoms, said ester having hydrophillic properties. v 17. A neutralized sulphuric acid ester of apolyhydric' alcohol, wherein the hydrogen of at least one hydroxy group ,of the alcohol is replaced by an acyl radical with at least four carbon atoms, said ester having hydrophile properties.

18. As; new chemical compoundsjsulphonated mixed mono-coconut fatty acid esters of diethyl- 19. A mixture containing sulphonated mixed mono coconut fatty acid esters of diethylene glycol and mono coconut fatty acid esters of diethylene glycol and alkaline salts thereof. I

20. As new chemical compounds, sulphonated mono higher fatty acid esters of a glycol and salts thereof.

21. As new chemical compounds, sulphonated mono higher fatty acid esters of a polyglycol and salts thereof.

22. A mixture containing sulphonated mono higher fatty acid esters of a polyglycol and mono higher fatty acid esters of a polyglycol and salts thereof.

23. An ester of sulphuric acid and an aliphatic polyhydroxy substance, wherein the hydrogen of at least one hydroxy group is replaced by an acyl radical of a normally liquid fatty acid, -and wherein the hydrogen of at least one other hy droxy group is replaced by a sulphate radical.

-BENJAMIN R. HARRIS. 

